Category: 32993-05-8

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Syntheses, structures, and electronic interactions of dicyanamide/tricyanomethanide-bridged binuclear organometallic complexes

Dicyanamide-bound mononuclear compounds Cp(dppe)FeN(CN)2 (3) and Cp(PPh3)2RuN(CN)2 (4) were isolated in high yields by the reactions of Cp(dppe)FeCl (1) and Cp(PPh3)2RuCl (2), respectively, with excess sodium dicyanamide. Compounds 3 and 4 are excellent precursors for the design of dicyanamide-bridged binuclear complexes [{Cp(dppe)Fe}2N(CN)2](SbF6) (5) and [{Cp(PPh3)2Ru}2N(CN)2] (SbF6) (6) by the incorporation with 1 and 2, respectively. Controlling oxidation of 5 with ferrocenium hexafluorophosphate afforded the mixed-valence compound [{Cp(dppe)Fe}2N(CN)2](PF6)2 (5a) which exhibits a broad absorption band in the near-infrared region (centered at 1500 nm, epsilon = 750 cm-1 M-1) due to the intervalence charge transfer of Robin and Day class II mixed-valence system. Tricyanomethanide-bound mononuclear compounds Cp(dppe)FeC(CN)3 (7) and Cp(PPh3)2RuC(CN)3 (8) were prepared by the same methods as 3 and 4 using potassium tricyanomethanide as the starting material instead. The tricyanomethanide-bridged binuclear complexes [{Cp(dppe)Fe}2C(CN)3](CF3SO3) (9) and [{Cp(PPh3)2- Ru}2C(CN)3](SbF6) (10) were prepared by the reactions between 7 and 1 and between 8 and 2, respectively. Cyclic voltammograms of the dicyanamide/tricyanomethanide-bridged binuclear complexes showed stepwise reversible one-electron oxidation waves with the potential separation of the two redox couples in the range 0.14-0.25 V, indicating the demonstrably electronic communication is operative between the organometallic components through a dicyanamide/tricyanomethanide spacer with metal…metal distances more than 7.8 A. Furthermore, the electronic coupling transmitted by the tricyanomethanide is appreciably greater than that by the dicyanamide. The complexes 3-10 were characterized by elemental analysis, IR, UV-vis, 1H and 31P NMR, and ES-MS. The crystal structures of 3 and 5-9 were determined by X-ray crystallography.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Syntheses and quadratic hyperpolarizabilities of some (pyridylalkynyl)metal complexes: Crystal structures of [Ni{2-(C?C)C5H3NNO2-5}(PPh 3)(eta-C5H5)], [Au{2-(C?C)C5H3NNO2-5}(PPh3)] and [Au{2-(C?C)C5H4N}(PPh3)]

The complexes [Ru{2-(C?C)C5H3NR-5}(PPh3) 2(eta-C5H5)] (R = NO2 1 or H 2), [Ni{2-(C?C)C5H3NR-5}(PPh3)-(eta-C 5H5)] (R = NO23 or H 4) and [Au{2-(C?C)C5H3NR-5}L] (L = PPh3, R = NO2 5 or H 6; L = PMe3, R = NO2 7) have been synthesized and 3, 5 and 6 structurally characterized; no significant increase in quinoidal vinylidene contribution to the acetylide ground-state structure is apparent on progression from structurally characterized phenylacetylide complexes to the new pyridylacetylide complexes, or upon replacement of 5-H by 5-NO2 in progressing from 6 to 5. The molecular quadratic optical non-linearities of 1-7 have been determined by hyper-Rayleigh scattering (HRS). The HRS measurements at 1064 nm are consistent with an increase in beta upon replacement of phenyl by an N-heterocyclic ring (replacing a nitrophenylacetylide by a nitropyridylacetylide ligand) for the ruthenium and gold systems, but with no change for the nickel complexes, and with an increase in non-linearity upon replacement of PMe3 by PPh3 in progressing from 7 to 5. The bulk second-order susceptibilities of the series have been determined by Kurtz powder measurements at 1054 nm, with the only significant response (about eight times that of urea) being that of 3; this complex was the only one of the three structurally characterized to pack non-centrosymmetrically in the crystal lattice. Electrochemical data for 1-4 have been obtained; comparison to analogous nitrophenylacetlylide complexes reveals that replacing nitrophenylacetylide by nitropyridylacetylide leads to a significant increase in MII/III oxidation potential for the ruthenium complexes, but to no change for the nickel examples. The parameter EoMII/II -EoNO2/NO2 – was evaluated for 1-4, results for M = Ru vs. Ni being consistent with experimentally determined non-linearities, i.e. smaller DeltaEo and larger non-linearities for ruthenium vs. nickel.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article£¬once mentioned of 32993-05-8, Product Details of 32993-05-8

Synthesis of ruthenium vinylidene complexes with dppe ligand and their cyclopropenation reaction

A number of cationic ruthenium vinylidene complexes [Ru]=C=C(Ph)CH2R+ ([Ru]=(eta5-C5H5)(dppe)Ru, dppe=Ph2PCH2CH2PPh2, 5a, R=CN; 5b, R=C6F5; 5c, R=Ph; 5d, R=p-C6H4CN; 5e, R=p-C6H4CF3; 5f, R=1-C10H7; 5g, R=CO2CH3) are prepared from electrophilic addition of organic halides to the acetylide complex [Ru]-CCPh at the boiling point of CHCl3. Complex 5g?, prepared at room temperature, displays similar spectroscopic property as that of 5g but is easily hydrolyzed to give [Ru]COCH2Ph (6). Cyclopropenation of the organic vinylidene moiety of 5a-5f is accomplished in acetone by deprotonation of 5 with n-Bu4NOH yielding the neutral cyclopropenyl complexes (7a, R=CN; 7b, R=C6F5; 7c, R=Ph; 7d, R=p-C6H4CN; 7e, R=p-C6H4CF3; 7f, R=1-10H7). Protonation of 7b-7f regenerates the corresponding vinylidene complexes. In the presence of allyl iodide, opening of the three-membered ring of 7a, followed by a subsequent oxidative coupling reaction, gives a dimeric dicationic product {[Ru]=C=C(Ph)-CHCN}2+2 (9a). In the processes of preparing the starting material Cp(dppe)RuCl for the acethylide complex, two dppe complexes Ru(dppe)2Cl2 (2) and [Cp(dppe)RuCl]2 (3) are isolated. Molecular structures of complexes 2, 3, 6, and 7b have been confirmed by X-ray diffraction analysis.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article£¬once mentioned of 32993-05-8, COA of Formula: C41H35ClP2Ru

Difluoromethylation of Terminal Alkynes by Fluoroform

The difluoromethylation of terminal alkynes through the use of fluoroform as a source of difluorocarbene is described. The choice of solvents and bases was found to be crucial for the transformation. A series of terminal alkynes 1 were nicely converted into the corresponding difluoromethyl alkynes 2 using potassium tert-butoxide in n-decane in moderate to good yields. Functional groups such as methoxy, dimethylamino, and bromo as well as phenyl, heteroaryl, and sterically demanding naphthyl were well tolerated under the reaction conditions. One-step transformations of difluoromethyl alkynes 2 to difluoromethylated isoxazoles 3 and 1,2,3-triazoles 4 were also achieved.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Phenanthroline-appended porphyrazines: Synthesis and conversion into solitaire Ru(II) complexes

Unsymmetrical porphyrazines (tetraazaporphyrins) bearing a single bidentate phenanthroline chelating group M[pz(t-butylphenyl)6phen] have been prepared by the base-catalyzed cross condensation of 3,4-bis(4-tert-butylphenyl)pyrroline-2,5-diimine (in excess) with 6,7-dicyanodipyridoquinoxaline. Treatment of these centrally metalated (M = Mg, Zn) ligands with various Ru(II) salts has yielded several bimetallic complexes including the first coordinatively linked porphyrazine trimer. The optical properties of these complexes are shown to be a function of the additional ligands surrounding the asymmetric ruthenium center.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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CYCLOPENTADIENYL-RUTHENIUM AND -OSMIUM COMPLEXES V. SYNTHESIS, REACTIVITY AND CRYSTAL STRUCTURE DETERMINATION OF CARBONYLCHLORO(eta-CYCLOPENTADIENYL)-(TRIPHENYLPHOSPHINE)RUTHENIUM(II)

CpRuCl(CO)PPh3 is formed as the result of refluxing CpRuCl(PPh3)2 in ethylene glycol (yield up to 15percent).A dissociation process is postulated with liberation of one PPh3 molecule and simultaneous rearrangement of the cation formed earlier: +Cl- -> CpRuCl(CO)PPh3 + PPh3.CpRuCl(CO)PPh3 reacts reluctantly with the alkoxy anion to give CpRuH(PPh3), in contrast to CpRuCl(PPh3)2, which undergoes very facile transformation into CpRuH(PPh3)2.The structure of CpRuCl(CO)PPh3 has been determined by the single-crystal X-ray diffraction method.The compound is triclinic, space group P<*>, a 9.378(2), b 10.584(2), c 16.590(4) Angstroem, alpha 126.11(1), beta 55.91(1), gamma 101.49(1) deg .The unit cell contains both R and S enantiomers.A shorter distance of the Ru-Cl bond has been noted in CpRuCl(CO)PPh3 (2.396 Angstroem) in comparison with the Ru-Cl distance in CpRuCl(PPh3)2 (2.453 Angstroem).This causes a diminishing tendency to lose a chloride ion and as a result, nucleophilic attack of RO- on CpRuCl(CO)PPh3.

The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 32993-05-8 is helpful to your research., Electric Literature of 32993-05-8

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Efficient transfer of dithiolene ligands from nickel to cyclopentadienyl ruthenium complexes

The reaction of [CpRu(PPh3)2Cl] with [Ni(S2C2Ph2)2] in refluxing toluene produces the purple salt [CpRu(S2C2Ph2)(PPh3)][Cl], containing a rare example of a cationic dithiolene complex, in excellent yield. Chemical or electrochemical reduction of [CpRu(S2C2Ph2)- (PPh3)][Cl] causes a colour change to blue and formation of the corresponding neutral species [CpRu(S2C2Ph2)(PPh3)]. In contrast the reaction of [CpRu(CO)2Cl] with [Ni(S2C2Ph2)2] under similar conditions was unsuccessful, but dithiolene transfer could be induced at room temperature by the use of Me3NO as a decarbonylating agent. In this case the neutral paramagnetic complex [CpRu(S2C2Ph2)(CO)] was formed, together with a crystallographically characterised dinuclear compound [Ru2(mu-S2C2Ph2)(mu-CO)(CO)Cp2]. The different outcomes of these reactions are related to the sigma-donor and pi-acceptor properties of the ligands.

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.HPLC of Formula: C41H35ClP2Ru. In my other articles, you can also check out more blogs about 32993-05-8

Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

Application of 32993-05-8, Chemistry can be defined as the study of matter and the changes it undergoes. You¡¯ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a patent, introducing its new discovery.

Synthesis of cyclopentadienyl ruthenium complexes containing 5-membered N-heterocyclic thiolates

Mononuclear ruthenium-thiolate complexes of structural type CpRu(PPh 3)2SR (1) [R = 2-imidazolyl (a), 1-methylimidazolyl (b), 5-methyl-1,3,5-thiadiazolyl (c) and 5-methyl-4H-1,2,4-triazolyl (d)] are accessible from the reaction of CpRu(PPh3)2Cl with the corresponding thiolate anions. Reaction of CpRu(PPh3)2Cl with the heterocyclic-thiolate anions in the presence of the bisphosphine ligands affords CpRu(P-P)SR [P-P = bis(diphenylphosphino)methane; dppm (2), bis(diphenylphosphino)ethane; dppe (3)]. If CO gas was bubbled through a THF solution of 1b, the complex CpRu(PPh3)(CO)S(C4N 2H5) (4b) is produced. These ruthenium-heterocyclic thiolate complexes have been characterized by elemental analysis, spectroscopy (IR, 1H, 31P{1H} NMR and MS) and cyclic voltammetry for some samples. The solid-state structures of 3a and 3b are determined by single-crystal X-ray structure analysis.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Syntheses of complexes containing substituted 4-ethynylquinolines or 1-azabuta-1,3-dienes by addition of imines to a cationic butatrienylidene-ruthenium complex

Reactions of [Ru(=C=C=C=CH2)(PR3)2Cp]+ (R=Ph or OMe) with arylimines ArN=CH(C6H4R) afford either substituted quinolines, Ru{CCC9H4RN(Ar)}(PR3)2Cp, by attack of the terminal carbon of the butatrienylidene ligand at the imine carbon, followed by C-C bond formation between the ortho carbon of the N-aryl group and Cgamma of the unsaturated carbene, or 1-azabuta-1,3-dienyl complexes, formed by cycloaddition of the N=CH group to Cgamma=Cdelta of the carbene, followed by opening of the resulting four-membered ring. Some product dependence on the nature of the substituents in the N- and C-aryl groups is found. The N atoms in the products are strongly basic, being readily protonated, methylated or aurated. The molecular structures of nine complexes are reported, together with that of a new modification of RuCl{P(OMe)3}2Cp.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Synthesis and characterisation of unsymmetrical metal (Ru11, Os”) and ferrocenyl complexes of l,3,5-triethynylbenzene

A series of complexes featuring metal (/ra;w-[RuCl(dppm)2], fra/-[OsCl(dppm)J or [Ru(r)-CjHs)(PPh3)2]) and ferrocenyl (C5H5FeC5H4) units unsymmetrically arranged around the periphery of a 1,3,5-triethynylbenzene core have been synthesized in good to reasonable yields by various synthetic routes. A crystal structure determination of/ra//5-[(C5HjFeC5H4OC)2C6Hj{OCRu(dppm)2CI}] shows that the two ferrocenyl units are positioned on the same side of the trisubstituted aromatic core and that all three ethynyl linkages are bent ‘down’ out of the plane of the central ring. Electrochemical studies show that in the heteronuclear coupling of osmium(n) or ruthenium(n) fragment(s) with ferrocenyl unit(s) the oxidation of Os” or Ru” precedes that of the ferrocene unit(s). In addition, whereas in diruthenium or diosmium complexes the oxidation of the two metal centres proceeds separately, in the diferrocenyl complexes the oxidation of the two ferrocene units occurs at the same potential values. This result shows that on appending different groups to the same skeletal core (namely, triethynylbenzene) some can interact electronically (the Ru”- and Os”-containing fragments) whereas others do not (the ferrocenyl units). The Royal Society of Chemistry 2000.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI